Treatment of drying oils



Pratt and Henry G. Berger.

that if the catalytic bodying reaction is carried Patented July 31, 1945UNITED STATES PATENT OFFICE 'raas'rmax'r F DRYING 0115 Henry G. Berger,George S. Crandall, and John F.

Socolofsky, Woodbury, Socony-Vacuum Oil Company, Incorporated, acorporation of New York No Drawlng. Application June 5, 1942.

Serial No. 445,970

I 8 Claims.

This invention relates to a process for con-" version ,of drying oils tobodied or polymerized products suitable for preparation of liquidcoating compositions such as varnishes and the like.

It has been common practice in the art for many years to body dryingoils, such as tung V from bodying of the less active drying oils. The

high-grade drying oils, such as tung and perilla oils, may be cooked tothe desired body without seriously affecting their value as film-formingagents. However. even the better oils are affected by excessive heattreatment.

According to our present process, drying oils are bodied catalyticallyby treatment in the presence of a polymerization catalyst to producebodied oils suitable for the preparation of liquid coating compositions.It is known that a variety of polymerization catalysts will effectpolymerization of drying oils, and such processes have been proposed forthe manufacture of compositions to be used as lubricants. These priorproc- 'esses involve catalytic polymerization followed by removal of thecatalyst when the desired stage of polymerization hasbeen'reached. The

products so produced arenot suitable for use in varnishes and otherliquid coating compositions since the films, if any, formed therefromare not resistant to frosting and have other disadvantages.

Processes for the production .of valuable catalytically bodied oils aredescribed in Patent No.

N. J.,' assignors to below 300 1''. if a sumcient degree of I bodying isattained and the action of the catalyst is then arrested, whereupon theoil may be blended with resins, .thinned and driers and the like added.In general, a body of at least 2-6 (Gardner- Holdt scale) should beattained before arresting the action of' the catalyst. That is, for mostpurposes. the oil should be catalytically bodied to a stage between Z-6and gelation by catalytic action. If the treated oil has a bodysubstantially below z-s when catalytic bodying is arrested, there is astrong possibility that films formed therefrom will become frosted. Thesaid prior patent of Pratt and Berger described varnishes prepared fromdrying oils bodied catalytically at temperatures below 300 F. andpointed out that these varnishes-formed frosted films. The experimentalwork of the present inventors provides an explanation of this findingand provides a means by which the noted disadvantages may be overcome.Oils bodied catalytically at the lower temperatures (below 300' F.) maynot be reactedto asumcient extent to provide the desired body becauseadditional body- 28 ing accompanies the necessary heating to dissolvethe resin. varnishes can be made from oils bodied to not more than Z-5Gardner-Holdt scale) by low temperature catalysis. If a greater body isachieved by catalytic'means, gelation occursduring heating to dissolvethe resin unless steps described herein are taken. But oils bodied toZ-5catalytically form varnishes that give frosted films. According to thisinvention an inactivator for the catalyst is added when a drying oilcontaining a polymerization catalyst has achievedthedesired body. Thisgelation inhibitor makes it possible to use oils bodied to an extentsutncient that the varnishes prepared therefrom 2,316,187, issued April13, 1943, to Malcolm I". 7

It is there disclosed out at temperatures of about 30051". or above,bodied oils of suitable properties are obtained.

We have now discovered that catalytic bodying.

may be satisfactorily conducted at lower temperatures, good resultsbeing obtained at room temperature, it the reaction is conducted in themanner described below.

The present invention is based on the discove y that satisfactoryvarnishes :can be made from drying oils catalytically bodied attemperatures oil to the desired body in a reasonable time when presentin concentrations which will not adversewill form hard, lustrous.transparent films; 1. e.

substantially greater than 2-5. Thus; an oil may he allowed to bodycatalytically until it has reached a body of more than Z-6+ or untilgelation is imminent before addition of inhibitor and subsequentblending withresin. By thisprocedure varnishes of body A to K at non-'volatile have been produced and after addition of the conventionaldriers, the resultant films drle clear and hard.

In practicing the inventionrwe use any of the known polymerizationcatalystsesuitable for the purpose from the standpoint of converting the1! affect films formed therefrom. This is a practical limitation on theprocess from a commercial tivity of the drying oil and catalystconcentration (including catalyst activity).

Obviously, any process within the scope of the invention must involveadjustment of the several variables and critical or optimum conditionsgenerally applicable are impossible to formulate. In general, wepreferto use the more active polymerization catalysts, for example, those ofthe Frie del-Crafts type oi metal halides, with particular preferencefor boron fluoride; although many other catalysts, such as hydrogenfluoride, titanium tetrachloride and other well-known polymerizationcatalysts may be used to advantage.

The inactivators or inhibitors are of varied nature. Water is anexcellent lnactivator and is aavantageously used in amounts on the orderof 1% based on the weight of the oil being treated, Ammonia, calciumcarbonate, pyridine, quinoline,

.isoquinoline, tri-amyl amine and other amines are also valuable for thepurpose of inactivating the catalyst. Much research has been conductedon catalysis of polymerization reactions in general and many agents areknown which have the effect of rendering polymerization catalystsinactive. The theory has been proposed that the inactivators arecompounds having a greater tendency to form addition compounds with thecatalyst than does the material being polymerized. The choice of aparticular inactivator must be determined by a number of factorsincluding nature and concentration of catalyst and use to be made of thebodied oil. The drlers normally employed in var- 'nishes are also goodinactivators but these are preferably used only where resin is dissolvedin the oil before bodying.

Our process may be exemplified by the catalytic bodyin of oiticica oiland of an oiticica oil-ester gum varnish base with boron fluoride atroom temperature.

The oil is uniformly mixed with the catalyst under non-gellingconditions. The catalyzed oil is collected in storage containers andallowed to stand at atmospheric temperaturesuntil the desired, degree ofpolymerization is attained. No agitation nor dilution of the reactionmaterials is required. The time required for the oil to attain thedesired body is naturally dependent upon the activity of the oil beingtreated, the concentration'of the catalyst and the temperature ofstorage. For illustrative purposes, the following table gives the timesrequired for raw oiticica oil catalyzed with various quantities of boronfluoride to attain a body of 2-5 on Gardner-Hodt scale =98.5 poises) andto reach gel stage when stored at atmospheric temperature.

Thus, the concentration of catalyst may be so tion is stopped. Insteadof resorting to the more drastic and complex procedures of dilution andextraction as practiced in the polymerization. of oils for lubricationpur loses, we stop the catalytic action by the addition of smallquantitiesof inactivators. Examples of effective inactivators are water(1%) ammonia, quinoline or isoquinoline (0.3%), and amines. Water, whenused under these conditions. does not destroy the catalyst as isevidenced by the fact that it may be expelled by heating, thus restoringthe activity of the catalyst. I

When applied to the catalytic bodying of varnish base, the resin and oilare blended with Just sufflcient heating to attain a homogeneous mixture(top temperature approximately 300 F.) and then subjected to the. sametype of treatment as used for the treatment of the drying oil.

The products obtained by this process may be used as bodied oils in themanufacture of varnishes. They may be used as prepared or, after theaddition of inactivator, they may be stored and utilized as desired.

Our process is superior to the prior art in that it is easilycontrolled; the concentration of catalyst used is not critical and maybe varied over rather wide ranges: no diluent is required and nocomplicated after-treatment is required.

Example I Raw oiticica oil 99.82 parts andboron fluoride 0.18 part werethoroughly mixed in a mixing unit of the type described in Patent No.2,238,864, havlng a suitable injection valve. The catalyzed oil wasplaced in a closed container and stored at prevailing room temperature(max. 92 F., min.

62F.) and the body of the oil determined at frequent intervals with aGardner-Holdt viscometer. The body of the oil immediately afterpreparation was Y =l7.6 poises), after 8 hours Z-3 =46.3

poises) after 14 hours z-4 (=63.4 poises) after 25 hours Z-5 (=98.5poises) after 37 hours Z-6, and after 45.5 hours gelation took place.

Example 11 Example III A. varnish base consisting of 33.3 parts of estergum and 66.8 parts of raw oiticica oil was heated for 15 minutes from 74F. to 267 F. to completely dissolve the ester gum. This mixture of resinand oil was then mixed uniformly with 0.1 port of boron fluoride inthemixing equipment referred to in Example I. After storage for 7 days. asample ofthe product was thinned with petroleum thinner and suitabledriers added (0.76":- Pb, 0.051% Mn. and 0.069% Co, based on oilcontent). A varnish having very desirable properties was obtained inthis way as shown by the following characteristics:

Body. at 50% non-Vela! tile C (Gardner-Holdt scale) Drying time:

Dust free hours 1 /4 Tack free do 2 Hard Overnight Film Hard Waterresistance Excellent Example IV To oiticica oil containing 0.1% boronfluoride was added 0.3% isoquinoline at body Z-l (=2'7.0 poises). After134 days storage, the body of this sample was still Z-1. A sample of thesame catalyzed oil without addition of an inactivator gelled in 3 days.

- Example V To oiticica oil, containing 0.08% boron fluoride, was added1.0% of water at an oil body of Z--1+ and after 30 days it was Z-2.After 133 days the body of this sample was Z-2+. A sample of the sameoil without the addition of an inactivator gelled in 5 days. theextended storage period may have been due to loss of water byevaporation:

Example VI Raw oiticica oil 99.92 parts and boron fluoride 0.08 partwere thoroughly mixed as described in Example I. The oil was stored atroom temperature until a body of Z-6 was obtained at which time 0.3%triamylamine was added. A 25 gallon varnish was then made fromthiscatalytically bodied oil by dissolving one part ester gum in two partsoil. 'After thinning to 60% non-volatile with petroleum thinner andadding 0.75% Pb., 0.05% Mn, 0.075% Co (basedon oil content) theresultant varnish had a body of J and drieddust free in 1 hour, tackfree in 1 /4 hours and hard over night. The dried film was clear andhard.

We claim:

1. The process which comprises polymerizing oiticica oil containingboron fluoride at a temperature not substantially above about 300 F. toa desired body and arresting polymerization of said on by additionthereto of a small quantity-of quinoline.

2. The process which comprises polymerizing oiticica oil containingboron ,fluorid at a temperature not substantially above about 300 F. toa desired body and arresting polymerization of said The slight increasein body over oil by addition thereto of a small quantity ofisoquinoline. 1

3. The process which comprises polymerizing a drying oil containingboron fluoride at a temperature not substantially above about 300 F. toa desired body and arresting polymerization of said oil by additionthereto of a small quantity of an inactivator for said boron fluorideselected .from the group consistin of quinoline and isoquinoline.

4. The process whichcomprises polymerizing a drying oil containing aFriedel-Crafts type polymerization catalyst at a temperature notsubstantially above about 300 F. to a desired body and arrestingpolymerization of said oil by addition thereto of a small quantity ofquinoline.

5. The process which comprises polymerizing a drying oil containing aFriedel-Crafts type polymerization catalyst at a temperature notsubstantially above about 300 F. to a desired body and arrestingpolymerization of said oil by addition thereto'of a small quantity ofisoquinoline.

6. The process which comprises polymerizing a drying oil containing aFriedel-Crafts type. polymerization catalyst at a temperature notsubstantially above about 300 F. to a desired body and arrestingpolymerization of said oil by addition thereto of a small quantity of.an inactivator for said catalyst selected from the group consisting ofquinolin and isoquinoline.

'7. Th process which comprises polymerizing a I drying oil containing apolymerization catalyst of the Friedel-Crafts type at a temperature notsubstantially above about 300 F. to a body not substantially lower than2-6 (Gardner-Holdt scale) and arresting polymerization of said oilbefore gelation thereof occurs by addition thereto of an inactivator forsaid catalyst selected from the group consisting of quinoline andisoquinoline.

8. In a process of preparing a liquid coating composition, the stepswhich comprise polymerizing a drying oil containing a polymerizationcatalyst of-the Friedel-Crafts type at a temperature not substantiallyabove about 300 F. to a body not substantially lower than 2-6(Gardner-Holdt scale), arresting polymerization of said oil beforegelation thereof occurs by addition thereto of an inactivator for saidcatalyst selected from the group consisting of quinoline andisoquinoline and thereafter adding resin, thinner and dried to form thesaid composition.

HENRY G. BERGER. GEORGE s. cRANnnL. JOHN F. socoLor'sKY.

